Cationic starch product in liquid form

ABSTRACT

Novel liquid cationic starch derivatives and methods for their preparation are described. The derivatives, prepared by reaction of starch with epichlorohydrin-ammonium hydroxide condensates, are useful as additives in the manufacture of paper wherein they increase the retention of inorganic pigments by the cellulose pulp and strengthen the resulting paper.

United States Patent Jarowenko et a1.

[54] CATIONIC STARCH PRODUCT IN LIQUID FORM [72] Inventors: Wadym Jarowenko, Plainfield; Morton W.

Rutenberg, N. Plainfield, both of NJ.

[73] Assignee: National Starch and Chemical Corporation, New York, NY.

[22] Filed: Feb. 27, 1970 [21] Appl.No.: 15,199

Related US. Application Data [63] Continuation-impart of Ser. No. 811,649, Mar. 28,

1969, abandoned.

[52] US. Cl. ..260/233.3 R, 106/213, 162/175, 260/233.5 [51] Int. Cl. ..C08b 19/06 [58] Field ofSearch ..260/233.3, 233.5; 106/213; 162/ l 75 [56] References Cited UNITED STATES PATENTS 3,247,048 4/1966 Gaertner 162/164 [15] 3,666,75 l [4 1 May 30, 1972 Primary Examiner-Donald E. Czaja Assistanl Examiner-M. l. Marquis Att0rneyThOmas B. Graham [57] ABSTRACT Novel liquid cationic starch derivatives and methods for their preparation are described. The derivatives, prepared by reaction of starch with epichlorohydrin-ammonium hydroxide condensates, are useful as additives in the manufacture of paper wherein they increase the retention of inorganic pigments by the cellulose pulp and strengthen the resulting paper.

7 Claims, No Drawings CATIONIC STARCI'I PRODUCT IN LIQUID FORM RELATED APPLICATIONS:

BACKGROUND OF THE INVENTION:

Cationic starch derivatives are useful as additives in a variety of industrial application. For example, cationic starch derivatives are often used in the paper manufacturing industry and in other industries as flocculating agents to disperse colloidal solutions. Moreover, they are particularly useful as.

beater and/or headbox additives in the manufacture of paper wherein their inherent cauonic charge significantly improves the retention of inorganic pigments, as well as of starch, by the cellulose pulp and thereby substantially increases the strength of the finished paper. U. S. Pat. No. 2,813,093 which issued on Nov. 12, 1957 to C. G. Caldwell and O. B. Wurzburg describes the preparation of a dry cationic starch by the ethen'fication of starch molecules with a substituent radical containing a tertiary amino group. With dry cationic starches, however, it is ordinarily necessary to add water and heat or boil the resulting mixture so as to effect its dispersion before it can be utilized in most end use applications. Needles to say, there are many advantages in being able to prepare such cationic starch derivatives in liquid form. Thus, a distinct advantage of the liquid cationic starch products of this invention is their ready applicability which is attained without requiring their dispersion as by cooking or mixing with water prior to their use. Other advantages include, for example, the convenience afforded in being able to measure, by volume, the necessary concentration of cationic starch product which is to be used.

It is the prime object of this invention to provide a process for preparing cationic starch derivatives directly in liquid form. It is another object of this invention to provide a cationic starch derivative in liquid form.

Various other objects and advantages of this invention will become apparent from the further disclosure which follows:

DETAILED DESCRIPTION OF THE INVENTION:

X (III) wherein X is solnrtutl from the group consisting of n has a value of from to 5, Z is selected from the group consisting of -H, CHg-CHCH:OH, -CH -CHCHz-OStarch and R;

H OH Y is selected from the group consisting of OH, NH;, H R R -N N/ and --N:R A

groups wherein R is selected from the group consisting of alkyl, hydroxyalkyl and carboxyalkyl groups with the alkyl portion thereof containing from about one to about 4 carbon atoms and A represents an anion selected from the group consisting of chloride, bromide, iodide, phosphate and sulfate anions.

It is'to be noted in the 'aemial vine ar" is difiic ult to determine precisely. However, since these are condensation reactions, the probable forms may occur in varying proportions depending on reagent ratios and, to some degree, on reaction conditions.

It iswell known that the cationicity of primary, and tertiary amines is dependent upon the pH of the system. At'low pHlevels, these amines tend to be strongly cationic. At high'pI-I levels these amines do not ionize and are, in essence, non-ionic. Quaternary amines, on the other hand, are cationic under all pH conditions. By cationic starch" is meant a starch carrying a positive charge which causes attraction or migration to the cathode. By the term cationic starches as used in the specification and claims herein, we mean starch products which contain any of the amine groups listed herein and mixtures thereof. Such starches are characterized by higher cationicity than the base from which the derivative was prepared. The presence of other modifying groups, such as anionic groups, on the starch would tend to change the degree of cationicity of the product,'depending on the pH level of the system.

Accordingly, the products of our invention may properly be described as liquefied amine starch derivatives. In more detail, now, the process which leads to the preparation of these novel derivatives may proceed as follows. 7

The starch, whichcomprises the base material for the reaction with the epichlorohydrin-ammonium hydroxide condensate, can be selected from among a number of starch types. Suitable starches include unmodified starch, as well as acid modified, dextrinized, hydrolyzed, oxidized, and derivatized starches such, for example, as starch ethers and starch esters which still retain reactive sites. The ester groups may, however, by hydrolyzed in the alkaline medium depending upon the specific reaction conditions. These starches may be derived from any sources including corn, wheat, potato, tapioca, waxy maize, sago, or rice, as well as from the socalled high amylose starches. Similarly applicable are the amylose and amylopectin fractions of starch. The use of the term "starch" is thus intended to include any maylaceous sub stances, whether modified or unmodified, which still retain free hydroxyl groups.

The epichlorohydrin-ammonium hydroxide condensate which is used to react with the starch is prepared by admixing epichlorohydrin with aqueous ammonium hydroxide in approximately equimolar proportions while maintaining the temperature of the system below about 60 C. and thereupon agitating-the mixture for a period of from about 1.5 to 16 hours. Water may be used to dilute the reaction mixture if secondary desired. It is to be understood that the condensation reaction between the epichlorohydrin and ammonium hydroxide should go essentially to completion and may, thus, require a longer reaction period at lower temperatures and a shorter reaction period at higher temperatures approaching 40 C. It is desirable to obtain an essentially complete reaction between the epichlorohydrin and the ammonium hydroxide while avoiding any appreciable epichlorohydrin-ammonium hydroxide polymer formation. The condensation may be carried out at temperatures of from about 10 to 60 C., or higher. Preferably, a temperature of about 15 C. and a reaction period of from about 2 to 5 hours is used.

The proportions of epichlorohydrin and ammonium hydroxide which are used may vary within a range of from about 0.8

to 3 moles of epichlorohydrin to 1 mole of ammonium hydroxide. condensates prepared using substantially more than 3 moles of epichlorohydrin tend to be more difficult to prepare and are less satisfactory in the process of the present invention since they tend to cross-link the starch to an undesirable degree and may thus require the use of special precautionary measures. On the other hand, condensates prepared using less than 0.8 mole of epichlorohydrin per mole of ammonium hydroxide lack reactive sites. Optimum results are obtained with the use of about equimolar portions of the two reagents. When the condensation is completed, the resulting reaction product may be used as is, or it may be adjusted by evaporation or dilution to a solids content of at least about 10 percent, by weight. The evaporation is conducted under reduced pressure while maintaining the temperature at less than about 70 C. As an optional step, the pH of the liquid condensate may, if desired, be adjusted to a level of about 3.0 prior to its evaporation in order to prevent the occurrence of any further condensation reaction or polymer formation.

in reacting the starch with the epichlorohydrin-ammonium hydroxide condensate, the starch may be first suspended in water and the resulting suspension heated at temperatures from about 80 to 160 C. for a sufficient period of time to effect gelatinization of the starch. The concentration of the aqueous starch suspension may vary from about 1 part of starch to about 3 to 30 parts of water. Suspensions comprising 1 part of starch to about to parts of water are most satisfactory.

After gelatinizing the starch, the mixture is cooled to about 40 C., although temperatures from about 25 to 100 C. may also be used, and a sufiicient concentration of a base, such as an alkali metal hydroxide, quaternary ammonium hydroxide, tetramethyl guanidine, or the like, is thereupon added in order to maintain the mixture at a pH greater than ll during the subsequent reaction. In a variation of the above procedure, the alkali may, if desired, be added prior to the gelatinization of the starch. With stirring, the epichlorohydrin-ammonium hydroxide condensate, as prepared by the above-described procedure, is then added to the gelatinized starch and is allowed to react therewith at a temperature from about 35 to 45 C. for a period of about 4 to 18 hours until the reaction is complete. If necessary, additional water may be added to dilute the reaction mixture. Upon completion of the reaction, the mixture, if desired, may be acidified to a pH level of from about 5 to 6 using any convenient acid, with hydrochloric or sulfuric acids being preferred for economic reasons. With regard to the proportions of starch and epichlorohydrin-ammonium hydroxide condensate which may be utilized, we prefer to use about 1 part, by weight, of the condensate solids with about I to parts, by weight, of dry starch. The actual proportions chosen are dependent on the degree of conversion or fluidity of the particular starch used in the reaction. Thus, to achieve comparable retention performance, higher proportions of the epichlorohydrin-ammonium hydroxide condensate solids with respect to the starch are required where a thin boiling starch is used. On the other hand, where higher viscosity starches are used, lower proportions of the epichlorohydrin-ammonium hydroxide condensate solids with respect to the starch are required.

in a variation of the above described method for making the cationic starch products of our invention, we have found that they can also be prepared by a continuous process. In accordance with the latter process, a slurry is formed of the uncooked starch, water, reagent (the previously described epichlorohydrin-ammonium hydroxide condensate) and sufficient alkali to bring the pH of the slurry to about 11 throughout the course of the reaction. This slurry is then passed through a continuous cooker. The term continuous cooker" refers to a type of equipment well known in the starch processing field, and comprises equipment through which a starch slurry is passed on a continuous basis and subjected to heat, usually in the form of injected live steam, so that the starch is discharged in a completely gelatinized ("cooked") state. When used to make the starch derivative of our invention, the continuous cooker method results in the essentially simultaneous gelatinization of the starch and its reaction with the epichlorohydrin-arnmonium hydroxide condensate, with the liquid cationic starch product being discharged from the cooker in continuous fashion. One of the major advantages of this continuous method is in speed, the reaction taking place in fractions of a minute as contrasted to the hours required by the batch method at lower temperatures. Furthermore, the continuous method enables the practitioner to prepare the starch product at the site of its eventual application and thus have a continuous flow of product for immediate use.

While the proportion of reagent to starch is within the same magnitude as already described for the batch process, there are other conditions which require special care. Remembering that the degree of gelatinization of starch in a continuous cooker system is affected by a number of variables, including the alkalinity of the slurry, the speed at which the slurry passes through the cooker and the temperatures achieved, it is important that the starch be subjected to sufficient heat within the cooker so as to achieve gelatinization and reaction of the starch. Ordinarily, this requires that the starch slurry within the continuous cooker be heated to at least C. Preferably, the epichlorohydrin-ammonium hydroxide condensate should be added immediately before the starch mixture is passed through the cooker in order to avoid crosslinking of the starch granules.

If desired, the reaction of the starch with the epichlorohydrin-ammonium hydroxide condensate may be carried out in the presence of a cross-linking inhibitor which acts to reduce the occurrence of cross-linking during the reaction. Such inhibitors include, for example, ammonium hydroxide, ethylamine, diethylamine, ethanolamine, triethanolamine, and sodium chloroacetate. They may be present in a concentration of about i to 15 percent, by weight, based on the weight of the starch. Furthermore, we believe that when the reaction mixture is more extensively diluted with water and/or cross linking inhibitors are utilized, the resulting reaction tends to produce a major proportion of monostarch substituted derivatives, i.e. the products which are represented by Formula II and Formula [I] wherein both Xs" are hydrogen, as shown in the structural representation, hereinabove. Likewise, the use of a less dilute reaction medium and/or the complete omission or the use of smaller concentrations of crosslinking inhibitor would tend to result in the preparation of a major proportion of the tristarch substituted product as illustrated in Formula [II hereinabove, wherein each X in the latter formula represents the Starch radical. The remaining possibilities, i.e. the derivatives represented by Formulas l and ll and those derivatives represented by Formula II], wherein one of the "X" groups represents the H radical and the remaining X" group represents the Starch radical, will be produced in a mixture containing a major proportion of these latter types of derivatives under reaction conditions falling in between the two extremes called for in the previously described conditions with respect to the dilution and/or the use of cross-linking inhibitors.

Thus, it can be understood that any given reaction of starch with the epichlorohydrin-ammonium hydroxide condensate will produce a mixture of various liquid cationic starch derivatives coming within the scope of Formulas 1, I1 and III with the precise composition of each mixture being determined by the character of the epichlorohydrin-ammonia condensate, the extent of the dilution of the reaction mixture, and/or the concentration of the cross-linking inhibitor. Detrimental crosslinking can also be avoided or reduced by great dilution of the reaction mixture with water, or by the use of converted starches. Ordinarily, it would have been expected that a reaction of this type would result in substantial cross-linking along with undesirable gel formation. It is surprising, therefore, that satisfactory products can, in fact, be obtained with the novel process of this invention.

The liquid cationic starch derivative resulting from the above described process should have a solids content in the range of from about 1 to about 25 percent, by weight, depending largely upon the method of preparation and may be preserved against microbial deterioration by the addition of formaldehyde, phenolic bactericides, or other desired preservatives.

The novel products of this invention can be utilized as paper-making additives in order to improve the retention of starch and inorganic pigments by the stock, i.e. by the cellulose pulp, as well as to increase the strength of the paper. In practice, the cationic starch is introduced into the beater, hydropulper, stock chest, or headbox, or at any desired combination of the latter locations, at any point during the normal course of the papermaking process prior to the ultimate conversion of the wet pulp into a dry web or sheet, i.e. at any stage prior to passing the stock onto the drying stage. They may be employed in concentrations of from about 0.1 to about 0.5 percent, by weight, based on the solids content of the cationic starch product with respect to the dry weight of the dispersed pulp.

The following examples will further illustrate the embodiment of our invention. In these examples, all parts given are by weight unless otherwise noted.

EXAMPLE I This example illustrates the preparation of several of the novel liquid cationic starches of the present invention and also demonstrates their utility as pigment retention aids in the manufacture of paper.

Part A. An epichlorohydrin-ammonium hydroxide condensate was prepared by slowly adding 185 parts (2.0 moles) of epichlorohydrin to 120 parts (2.0 moles) of concentrated ammonium hydroxide (29 percent) in 1,000 parts of water. The temperature was maintained at about C. by the application of external cooling throughout the course of the addition. The mixture was agitated at room temperature for about 16 hours after which time it was evaporated to about 80 percent solids while under reduced pressure and while maintaining the temperature below 20 C.

Part B(l Fifty parts of thin boiling corn starch which had been prepared by reaction of raw corn starch with sodium hypochlorite solution until it had been converted to a degree known in the trade as 85 fluidity, were suspended in 250 parts of water, heated for 20 minutes on a boiling water bath, and cooled to 40 C. after which time 16.8 parts of a 50 percent, by weight, aqueous solution of sodium hydroxide was added. At this point, 31.5 parts of the epichlorohydrin-ammonium hydroxide condensate, as prepared in Part A hereinabove, were added with stirring while the temperature was maintained at 40 C. As the viscosity increased, the reaction mixture was gradually diluted by the addition of small portions of water. Thus, after 35 minutes, an additional 100 parts of water had been added while after 50 minutes a total of 250 parts of water had been 16.8 After 1.5 hours the system was acidified with 20 parts of concentrated hydrochloric acid. The final pH of the system was 5.2 and the resulting liquid cationic starch reaction product had a solids content of 13 percent, by weight.

Part B(2 Twenty-five parts of thin boiling waxy maize starch which had been prepared by reaction of raw waxy maize starch with aqueous mineral acid until it had been converted to a degree known in the trade as fluidity, were suspended in 250 parts of water, heated for 30 minutes on a boiling water bath, and cooled to 40 C., after which time 16.2 parts of a 50 percent, by weight, aqueous solution of sodium hydroxide was added. With stirring, 15.75 parts of the epichlorohydrinarnmonium hydroxide condensate, as prepared in Part A hereinabove, were added and the temperature was maintained at 40 C. for a total period of 18 hours. The system was then acidified with 20 parts of concentrated hydrochloric acid. The resulting liquid cationic starch reaction product had a solids content of l2 percent, by weight.

Part B((3). Twenty-five parts of thin boiling waxy maize starch which had been prepared by reaction of raw waxy maize starch with aqueous mineral acid until it had been converted to a degree known in the trade as 85 fluidity, were suspended in 250 parts of water and 16.2 pans of a 50 percent, by weight, aqueous solution of sodium hydroxide was added with stirring. While stirring was continued, the mixture was heated to 40 C. and maintained at that temperature for about 1 hour. At this point, 1.7 parts of diethylarnine followed by 15.70 parts of the epichlorohydrin-ammonium hydroxide condensate, as prepared in Part A hereinabove, were added and the reaction was continued at 40 C., with stirring, for a total of 16 hours. The system was then acidified with 20 parts of concentrated hydrochloric acid. The resulting liquid cationic starch reaction product had a solids content of 15 percent, by weight.

Pan 8(4). The procedure of Part (8)3 was repeated using 25 parts of thin boiling corn starch as described hereinabove with the exception, in this instance, that the addition of the diethylarnine was omitted. The resulting liquid cationic starch reaction product had a solids content of 15 percent, by weight.

In order to determine the effectiveness of these reaction products as pigment retention aids, each of the above described liquid cationic starches was added to the headbox during the normal course of a conventional papermaking process. In each case, the reaction product was added in a concentration of 0.25 percent, by weight, based on the solids content of the starch product with respect to the dry weight of the dispersed pulp. The cellulose pulp also contained 10 percent of titanium dioxide, based on the dry weight of the pulp. The degree of pigment retention, i.e. the percent, by weight, of the initially added pigment that was present in the resulting paper sheets in which these derivatives were homogeneously dispersed, was then determined by ashing the paper and weighing the resulting ash.

The following table presents the data obtained.

the data for the blank were obtained from a series of determinations. "Acidity adjusted with aluminum sulfate.

Thus, the above data clearly demonstrate the improved pigment retention which is achieved by the use of the novel liquid cationic starch derivatives of this invention.

In addition, the strength of the paper containing the liquid cationic starch was substantially increased as compared to the control sample.

This example illustrates the preparation of additional novel liquid cationic starches of the present invention utilizing a continuous cooker and also demonstrates their utility as pigment retention aids in the manufacture of paper.

Part A( l The epichlorohydrin-ammonium hydroxide condensate used herein was prepared as described in Part A of Example I with the exception that the evaporation step was omitted and the reaction was conducted so as to result in a condensate having about 39percent solids.

Part A(2). The epichlorohydrin-ammonium hydroxide condensate was a reaction product of 3 moles of epichlorohydrin and 1 mole of ammonium hydroxide. The preparation involved the slow addition of 287.6 parts of epichlorohydrin to 59.5 parts of concentrated (35percent) ammonium hydroxide solution which was dissolved in 350 parts of water while maintaining the temperature of the reaction mixture at 25 30C. by external cooling. The mixture was agitated at room temperature for about 18 hours after which time it was evaporated to about 86percent solids while under reduced pressure and while maintaining the temperature below 40 C.

Part 13(1). Seventyfive parts of waxy maize starch were slurried in 3,750 parts of water containing 8.5 parts of sodium hydroxide. To this slurry there was added 19.2 parts of the epichlorohydrin-ammonium hydroxide condensate, as prepared in Part A( l hereinabove. Thereafter, the resultant mixture was passed through a continuous cooker at a rate of about 1.1 gallons per minute which was adjusted to raise the temperature of the contents to about 150 C. These conditions allowed complete dispersion of the starch as well as its reaction with the epichlorohydrin-arnmonium hydroxide condensate. The resulting liquid cationic starch product which was discharged from the pressure cooker had a solids content of 2.0 percent by weight, and a final pH of l 1.2.

Part B(2). Seventy-five parts of potato starch were slurried in 3,750 parts of water containing 8.5 parts of sodium hydroxide. To this slurry there was added 38.4 parts of the epichlorohydrin-ammonium hydroxide condensate, as prepared in Part A( l hereinabove. Thereafter the resultant mixture was passed through a continuous cooker at a rate of 1.4 gallons per minute at a temperature of about 150 C. which allowed complete dispersion of the starch as well as its reaction with the epichlorhydrin-ammonium hydroxide condensate. The resulting liquid cationic starch product which was discharged from the cooker had a solids content of 2.8 percent, by weight, and a final pH of 10.9.

Part 8(3). Sixty parts of waxy maize starch were slurried in 1940 parts of water containing 4.8 parts of sodium hydroxide. To this slurry there was added 2.8 parts of epichlorhydrin-ammonium hydroxide condensate (3:1) as prepared in Part A(2), hereinabove. Thereafter, the resultant mixture was passed through a continuous cooker at the rate of about 1.0 gallon per minute which was adjusted to raise the temperature of the contents to about 150 C. These conditions allowed complete dispersion of the starch as well as its reaction with the epichlorohydrin-ammonium hydroxide condensate. The resulting liquid cationic starch product which was discharged from the cooker had a solids content of 2.2 percent, by weight, and a final pH of 10.5.

The effectiveness of these reaction products as pigment retention aids was determined according to the testing procedure described in Example 1.

The following table presents the data obtained.

Acidity adjusted with aluminum sulfate.

The above data, likewise, clearly demonstrate the improved pigment retention which is achieved by use of the novel liquid cationic starch derivatives of this invention which in this instance had been prepared utilizing a continuous cooker.

EXAMPLE 11 This example illustrates the preparation of a novel liquid cationic starch derivative using potato starch as the base for the reaction.

Ten parts of potato starch were suspended in 300 parts of waterand 8 parts of a 50 percent, by weight, aqueous solution of sodium hydroxide was added with stirring. While stirring was continued, the mixture was heated to 40 C. and maintained at that temperature for about 1 hour. At this point, 5.1 parts of the epichlorohydrin-ammonium hydroxide condensate, as prepared in Part A of Example 1 hereinabove, were added and the reaction continued for a total of 16 hours. The system was acidified with 20 parts of concentrated hydrochloric acid. The resulting liquid cationic starch reaction product had a solids content of 6 percent, by weight.

When tested as a pigment retention aid in the manner described in Example 1 hereinabove, it was found that this product permitted the retention of 60 percent, by weight, of titanium dioxide at pH 7.6 and 65 percent, by weight, of the latter pigment at pH 6.0. Improved retention was also observed at other pH levels.

In another preparation, the above procedure was repeated using 10 parts of potato starch while 1.36 parts of diethylamine were introduced just prior to the addition of the epichlorohydrin-arnmonium hydroxide condensate. The resulting liquid cationic starch product had a solids content of 5.6 percent, by weight.

When tested as a pigment retention aid in the manner described in Example 1 hereinabove, it was found that this product permitted the retention of 64 percent, by weight, of titanium dioxide at pH 7.6 and 71 percent, by weight, of the latter pigment at ph 6.0.

EXAMPLE 111 This example illustrates the preparation of additional samples of the novel liquid cationic starch products of this invention using raw waxy maize starch as the starch base.

Fifteen parts of raw waxy maize starch were suspended in 350 parts of water and 12 parts of a 50 percent, by weight, aqueous solution of sodium hydroxide were added with stirring. While stirring was continued, the mixture was heated to 40 C. and maintained at that temperature for 1 hour. At this point, 2.4 parts of diethylamine followed by 1.52 parts of the epichlorohydrin-ammonium hydroxide condensate, as prepared in Part A of Example 1 hereinabove, were added and the reaction continued for a total of 16 hours. The system was acidified to pH 5.0. The resulting liquid cationic starch product had a solids content of 6.4 percent, by weight.

When this product was tested as a pigment retention aid in the manner described in Example 1 hereinabove, it was found that it permitted the retention of 65 percent, by weight, of titanium dioxide with a paper stock which was at a pH of 7.6.

Similar pigment retention results were obtained with products which were prepared with diethylamine inhibitor using 10, 20, 30, 40, and 50 percent, by weight, respectively, of the epichlorohydrin-ammonium hydroxide condensate as based on the amount of dry starch. Comparable treatments based on raw waxy maize starch were prepared without diethylarnine being present in the reaction system and were found to yield highly cross-linked products.

EXAMPLE IV This example illustrates the attempted preparation of the novel liquid cationic starch products of this invention by means of a batch operation using temperatures and reaction periods outside of the specified ranges required for each of the latter variables.

Part A. An epichlorohydrin-ammonium hydroxide condenadding 92.5 parts (1.0 mole) of (1.0 mole) of concentrated ammonium hydroxide (29 percent) in 500 parts of water. The temperature was maintained at about C. by the application of external cooling throughout the course of the addition. The mixture was agitated at room temperature for about 16 hours, acidified to about pH 3.0 with dilute hydrochloric acid and evaporated to dryness while under reduced pressure and while maintaining the temperature below 20 C.

Part B. Forty parts of thin boiling waxy maize starch which had been prepared by reaction of raw waxy maize starch with aqueous mineral acid until it had been converted to a degree At this point, epichlorohydrin-ammonium hydroxide condensate whose preparation was described in Part A of the Example, were added with stirring, and samples of the reaction mixture were taken after a period of 0.5, 1.0, 2.0, and 20 hours, respectivetion of concentrated pH of the reaction product to a level of 4.0.

When tested as pigment retention aids in the manner described in Example 1 hereinabove, it was found that the first three products permitted the retention at pH 7.6, cent or less, by weight, of titanium dioxide. The product obtained by the use of a 20 hour reaction period was in the form of a gel, indicative of excessive crosslinking, and could not therefore be tested.

EXAMPLE V This example illustrates the preparation of two of the novel liquid cationic starch derivatives of this invention using potato starch as the base and wherein the epichlorohydrinammonium hydroxide condensates were prepared using other than equimolar proportions of the two reagents comprising the condensate.

Ten parts of potato starch were suspended in 300 parts of water and 8 parts of a 50 percent, by weight, aqueous solution of sodium hydroxide were then added with stirring. While stirring was continued, the mixture was heated to 40 C. and maintained at that temperature for about 1 hour. At this point, 5.1 parts of an epichlorohydrin-ammonium hydroxide condensate, prepared as described in Part A of Example I using 0.8 mole of epichlorohydrin and 1.0 mole of ammonium hydroxide, were added and the reaction was continued for a total of 16 hours. The system was then acidified with 20 parts of concentrated hydrochloric acid.

In another preparation which, in this instance used 10 parts of potato starch as the base for the reaction, the above procedure was repeated except that the condensate utilized was prepared by the reaction of 1.1 moles of epichlorohydrin with 1.0 mole of ammonium hydroxide.

When tested as pigment retention aids in the manner described in Example 1 hereinabove, each of the two reaction products displayed results comparable to those obtained with the liquid cationic starch products of Example 11.

Summarizing, our invention is thus seen to provide novel liquid cationic starch derivatives along with a process for their preparation. Variations may be made in proportions, procedures and materials without departing from the scope of this invention which is defined by the following claims.

What is claimed is:

l. A method for preparing an aqueous dispersion of a cationic starch derivative which comprises reacting, in aqueous hydroxide.

2. The method of claim 1, wherein said reaction is conducted at a temperature from about 35 to 45 C. and for a period of from about 4 to 1 8 hours.

3. The method of claim 1, wherein a cross-linking inhibitor reaction between the gelatinized starch gelatinization and starch-epichlorohydrin-ammonium hydroxide condensate reaction being conducted at a temperature of at least C.

6. The method of claim 5, wherein a crosslinking inhibitor is present during said reaction between the starch and the epichlorohydrin-ammonium hydroxide condensate.

7. The starch derivative prepared by the process of claim 5.

I t I II t 

2. The method of claim 1, wherein said reaction is conducted at a temperature from about 35* to 45* C. and for a period of from about 4 to 18 hours.
 3. The method of claim 1, wherein a cross-linking inhibitor is present during said reaction between the gelatinized starch and the epichlorohydrin-ammonium hydroxide condensate.
 4. The starch derivative prepared by the process of claim
 1. 5. A method for preparing an aqueous dispersion of a cationic starch derivative which comprises gelatinizing a starch and essentially simultaneously therewith, reacting from about 1 to 20 parts, by weight, of said gelatinized starch, in aqueous medium under alkaline conditions, with one part, by weight, of an epichlorohydrin-ammonium hydroxide condensate resulting from the condensation reaction at 10* - 60* C. of from about 0.8 - 3.0 moles of epichlorohydrin per mole of ammonium hydroxide; said essentially simultaneous starch gelatinization and starch-epichlorohydrin-ammonium hydroxide condensate reaction being conducted at a temperature of at least 120* C.
 6. The method of claim 5, wherein a crosslinking inhibitor is present during said reaction between the starch and the epichlorohydrin-ammonium hydroxide condensate.
 7. The starch derivative prepared by the process of claim
 5. 